CN102782847A - Resistance change device and memory cell array - Google Patents

Resistance change device and memory cell array Download PDF

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Publication number
CN102782847A
CN102782847A CN201180011998XA CN201180011998A CN102782847A CN 102782847 A CN102782847 A CN 102782847A CN 201180011998X A CN201180011998X A CN 201180011998XA CN 201180011998 A CN201180011998 A CN 201180011998A CN 102782847 A CN102782847 A CN 102782847A
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electrode
coating
oxide skin
filament
metal
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CN102782847B (en
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藤井章辅
松下大介
三谷祐一郎
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Kioxia Corp
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Toshiba Corp
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors
    • H10N70/24—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
    • G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
    • G11C13/0007—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements comprising metal oxide memory material, e.g. perovskites
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B63/00—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices
    • H10B63/20—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices comprising selection components having two electrodes, e.g. diodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B63/00—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices
    • H10B63/30—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices comprising selection components having three or more electrodes, e.g. transistors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B63/00—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices
    • H10B63/80—Arrangements comprising multiple bistable or multi-stable switching components of the same type on a plane parallel to the substrate, e.g. cross-point arrays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors
    • H10N70/24—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies
    • H10N70/245—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies the species being metal cations, e.g. programmable metallization cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/821—Device geometry
    • H10N70/826—Device geometry adapted for essentially vertical current flow, e.g. sandwich or pillar type devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/841—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/841—Electrodes
    • H10N70/8416—Electrodes adapted for supplying ionic species
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H10N70/883—Oxides or nitrides
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C2213/00—Indexing scheme relating to G11C13/00 for features not covered by this group
    • G11C2213/70—Resistive array aspects
    • G11C2213/79—Array wherein the access device being a transistor

Abstract

According to one embodiment, a resistance change device includes a first electrode including a metal, a second electrode, and an amorphous oxide layer including Si and O between the first and second electrode, the layer having a concentration gradient of O and a first peak thereof in a direction from the first electrode to the second electrode.

Description

Resistance variations device and memory cell array
The cross reference of related application
The application is the priority of the Japanese patent application of 2010-073697 based on the sequence number that also requires to submit on March 26th, 2010; By reference its full content is incorporated among this paper.
Technical field
The embodiment that describes among this paper relates in general to resistance variations device and memory cell (memory cell) array.
Background technology
Be sandwiched between the upper/lower electrode and comprise nickel (Ni) and oxygen (O) and wherein the concentration of O from bottom electrode towards the resistance switching metal oxide layer that top electrode increases; O in the resistance switching metal oxide layer electric current from power on extremely downwards during electrode through the Joule heat diffusion, form heavily doped Ni part thus partly.In this structure,, therefore be difficult to controlling resistance and change because the density unevenness of the O in the resistance switching metal oxide is even.
Summary of the invention
Generally, according to an embodiment, a kind of resistance variations device comprises: first electrode that comprises metal; Second electrode; And the amorphous oxide layer that comprises Si and O between said first and second electrodes, this layer has the concentration gradient and first peak value thereof of O in the direction from said first electrode to said second electrode.
A kind of memory cell array comprises: a plurality of first wirings, and it comprises metal and extends to first direction; A plurality of second wirings, it is to extending with the crossing second direction of said first direction; And a plurality of memory cells; It is set between said first and second wirings; In the said memory cell each comprises electro-resistance element and the rectifier cell that is connected in series; Wherein, said electro-resistance element comprises the amorphous oxide layer that comprises Si and O, and on the third direction that intersects with said first and second directions, has the concentration gradient and first peak value thereof of O.
A kind of resistance variations device comprises: a plurality of first electrodes, each said first electrode package containing metal and along the first direction setting; A plurality of second electrodes, it is along said first direction setting, and on the second direction that intersects with said first direction one by one towards each said first electrode; And the amorphous oxide layer that comprises Si and O between said first electrode and said second electrode, this layer has the concentration gradient and first peak value thereof of O on said second direction.
Description of drawings
Fig. 1 shows electro-resistance element;
Fig. 2 A and 2B show the composition of oxide skin(coating);
Fig. 3 A and 3B show the operation principle of electro-resistance element;
Fig. 4 A shows many-valued (multilevel) operation of electro-resistance element to 4D;
Fig. 5 shows electro-resistance element;
Fig. 6 shows the ionic radius of metallic element;
Fig. 7 shows the memory cell array;
Fig. 8 shows the resistance variations device; And
Fig. 9 and 10 shows the resistance variations memory.
Embodiment
(first embodiment)
Fig. 1 shows the view according to the electro-resistance element 10 of first embodiment.
In electro-resistance element 10, oxide skin(coating) 1 is sandwiched between two electrodes 2 and 3.
As electrode 2, can use to be selected from the for example metal of Ag, Ti, Ni, Co, Al, Cr, Cu, W, Hf, Ta and Zr.Also so that with any nitride or the carbide in the above-mentioned metal as electrode 2.In addition, can use at least a alloy that comprises in these metals.
As electrode 3, for example can use the wherein Si of heavy doping B.This is because the resistivity of Si can be set to 0.005 Ω cm or littler through heavy doping B.Electrode 3 for example is not limited to the wherein Si of heavy doping B, and can be the Si of other impurity that mix.The instance of impurity is As and P.Can also use known electrode material such as Ti, Ta, W and nitride thereof.
Oxide skin(coating) 1 for amorphous and comprise O and Si.In oxide skin(coating) 1, the concentration of O increases towards electrode 3 from electrode 2, and exists the concentration gradient of O wherein to have at least one zone of peak value.Just, exist the concentration gradient of O wherein on the stacked direction of oxide skin(coating) 1, to have at least one zone of peak value.In other words, oxide skin(coating) 1 comprises the low layer of the concentration of O wherein and the high layer of concentration of oxygen wherein, and the concentration of the layer that the concentration of O is high therein and oxygen wherein low layer between the border in the concentration gradient increase.Even when between electrode 2 and 3, applying voltage, the composition of O is also almost constant.This is owing to oxide skin(coating) 1 is an amorphous, thereby does not have crystal structure, and perhaps strong bond is incorporated into O to Si through covalent bond.The film thickness of oxide skin(coating) 1 is for for example arriving 300nm 1 (containing 1).When the dimension shrinks of electro-resistance element 10, the film thickness of oxide skin(coating) 1 is preferably as far as possible little.When considering this point, the film thickness of oxide skin(coating) 1 was preferably for 2 (containing 2) to 50 (containing 50) nm.
Fig. 2 A and 2B are the view that is used for explaining the concentration gradient of the O that comprises at oxide skin(coating) 1.The value of abscissa (in the drawing to the right) indicated concentration gradient, ordinate (in the drawing downwards) expression from electrode 2 to electrode 3 apart from x.
Shown in Fig. 2 A,, oxide skin(coating) 1 for example has composition SiO0 when comprising .1Layer (ground floor 4) and have composition SiO 0.5Layer (second layer 5) time, the composition of O raises 0.4 in the border between the ground floor 4 and the second layer 5.Under this state, concentration gradient has peak value in the border between the ground floor 4 and the second layer 5.In this case, the film thickness of the ground floor 4 and the second layer 5 is for example 50nm.
Equally, when oxide skin(coating) 1 has two peak values of concentration gradient, exist the 3rd layer 6, the three layers 6 concentration to be higher than the concentration of the second layer 5, shown in Fig. 2 B.Notice that the composition of the O in the 3rd layer 6 is 0.8.
Next, with the operation principle of explaining below according to the electro-resistance element 10 of this embodiment.Fig. 3 A and 3B are the view that is used to explain according to the operation principle of the electro-resistance element 10 of this embodiment.Operation principle is explained in the setting that will have a peak value through the concentration gradient that adopts the O in the oxide skin(coating) 1 wherein as an example.Comprise that through hypothesis oxide skin(coating) 1 ground floor 4 and the second layer 5 describe.
Shown in Fig. 3 A, when applying the electrode 2 that makes electro-resistance element 10 and become positive voltage with respect to electrode 3, the metal that is included in the electrode 2 is changed into ion.In oxide skin(coating) 1, metal ion is towards electrode 3 diffusions.Form filament (filament) 7 with this mode.Filament 7 has high conductivity, and this is because it is to be formed by metal.Therefore, the resistance of ground floor 4 reduces.Being formed in the border between the ground floor 4 and the second layer 5 of filament 7 stops.This is because the concentration of the O in the second layer 5 is higher than the concentration of the O in the ground floor 4, so the metal ion diffusion velocity reduces in the second layer 5.Note, through 3 supply weak currents read the value of resistance from electrode 2 to electrode.It shall yet further be noted that then tunnelling current flows through the second layer 5 if filament 7 only is formed into ground floor 4.
Shown in Fig. 3 B, when under this state, applying when making electrode 2 become negative voltage with respect to electrode 3, towards electrode 2 diffusions, thereby filament 7 disappears the metal ion that is present in the formation filament 7 in the ground floor 4 from electrode 3.As a result, the resistance of ground floor 4 increases.
Shown in Fig. 3 A, when applying the electrode 2 that makes electro-resistance element 10 once more and become positive voltage with respect to electrode 3, the metal that is included in the electrode 2 becomes ion, and these metal ions in oxide skin(coating) towards electrode 3 diffusions, form filament 7 thus.Just, make electrode 2 with respect to the voltage that electrode 3 is just becoming or change is negative, can in oxide skin(coating) 1, form filament 7 or filament 7 is eliminated from oxide skin(coating) 1 through applying.
Therefore, the setting state through will be for example wherein in oxide skin(coating) 7, forming filament 7 for ' 1 ' and the setting state that will wherein not form filament 7 be ' 0 ', two-value (binary) electro-resistance element 10 can be provided.Recorded information in electro-resistance element 10 thus.Note,, therefore can reduce the amount of the electric current of 3 supplies from electrode 2 to electrode because filament 7 is formed and does not extend to electrode 3.
Equally, through filament 7 is extended to electrode 3, and wherein filament 7 setting state that is formed into electrode 3 is ' 2 ', can obtain three values (many-valued) element." many-valued " representes that the number of its intermediate value (level) is three or more state.
In above-mentioned oxide skin(coating) 1, the concentration of O increases towards electrode 3 from electrode 2, and exists concentration gradient wherein to have at least one zone of peak value.Therefore, the composition of the O in the ground floor 4 of the electro-resistance element 10 of reference example such as Fig. 2 A and 2B explanation and the second layer 5 is than being different.Correspondingly, metal ion is different from the diffusion velocity of electrode 2 diffusion ground floor 4 and the second layer 5.Can realize many-valued electro-resistance element 10 through using this difference between the metal ion diffusion velocity.
To explain now and will be increased to three or more method (that is, obtaining the method for many-valued element) according to the number of the value of the electro-resistance element 10 of this embodiment.
Fig. 4 A, 4B, 4C and 4D are exemplary plot, and each figure shows when the I-E characteristic that applies when making electrode 2 with respect to the positive voltage of electrode 3 changes, and the counter structure of electro-resistance element 10.Note, comprise that through hypothesis oxide skin(coating) 1 ground floor 4, the second layer 5 and the 3rd layer 6 describe.
Because oxide skin(coating) 1 has the composition ratio of different O, metal ion changes at each interlayer from the speed of electrode 2 towards electrode 3 diffusions.
Fig. 4 A is the metal figure of the state of diffusion in oxide skin(coating) 1 not that shows electrode 2 wherein.In the time under this state, will making electrode 2 become positive voltage and be applied to electro-resistance element 10 and reach given voltage (V1) with respect to electrode 3, the metal of electrode 2 is changed into ion, and these metal ions form filament 7 in ground floor 4, shown in Fig. 4 B.Under this state, current value raises suddenly, shown in the filled circles in the Lower Half of Fig. 4 B.This is because in ground floor 4, form conduction filament 7, and this earth has reduced the resistance value of electro-resistance element 10.Being formed in the border between the ground floor 4 and the second layer 5 of filament 7 stops.This is because the concentration of the O in the second layer 5 is higher than the concentration of the O in the ground floor 4, thereby the metal ion diffusion velocity reduces in the second layer 5.
Then, apply the voltage (V2) that is higher than voltage V1, so that electrode 2 is just becoming with respect to electrode 3.Therefore, shown in Fig. 4 C, the metal ion that in ground floor 4, forms filament 7 spreads in the second layer 5, thereby filament 7 extends.Under this state, current value further raise (filled circles of the Lower Half among Fig. 4 C).This is because the length of conduction filament 7 further increases.Being formed in the border between the second layer 5 and the 3rd layer 6 of filament 7 stops.This is because the concentration of the O in the 3rd layer 6 is higher than the concentration of the O in the second layer 5, thereby the metal ion diffusion velocity reduces in the 3rd layer 6.
Subsequently, apply the voltage (V3) that is higher than voltage V2, so that electrode 2 is just becoming with respect to electrode 3.Therefore, shown in Fig. 4 D, the metal ion that in second electrode 5, forms filament 7 spreads in the 3rd layer 6, thereby filament 7 extends.Under this state, current value further raise (filled circles of the Lower Half among Fig. 4 D).This is because the length of conduction filament 7 further increases.Thus, filament 7 is formed into electrode 3 from electrode 2.
As stated, the state shown in Fig. 4 A, 4B, 4C and the 4D progressively changes about voltage V1, V2 and V3 with specific threshold.This can realize many-valued electro-resistance element 10.Note, through 0.1 (containing 0.1) for example to the value of scope stop voltage V1, V2 and the V3 of 15 (containing 15) V.When the size of electro-resistance element 10 is reduced to the size of about 50nm for example, the value of voltage V1, V2 and V3 preferably 0.1 (containing 0.1) scope to 6 (containing 6) V limit.
Likewise; When (promptly at the state shown in Fig. 4 B, 4C and the 4D; Wherein in oxide skin(coating) 1, form the state of filament 7) under apply when making electrode 2 become negative voltage with respect to electrode 3; Because the electric field that is applied, the metal ion that forms filament 7 spreads towards electrode 2 from electrode 3, so filament 7 can be eliminated.Just, can make electrode 2 become negative or become positive voltage and in oxide skin(coating) 1, form filament 7 or eliminate filament 7 through applying from oxide skin(coating) 1 with respect to electrode 3.Equally, through limiting the value that makes electrode 2 become this voltage of bearing with respect to electrode 3 the scope that for example-0.1 (contains-0.1) to-15 (containing-15) V.When the size of electro-resistance element 10 is reduced to the size of about 50nm for example, this magnitude of voltage preferably-0.1 (containing-0.1) scope to-6 (containing-6) V limit.
Correspondingly; Can be ' 0 ' through the setting state that for example will wherein in oxide skin(coating) 1, not form filament 7; The setting state that filament wherein 7 is formed up to ground floor 4 is ' 1 '; The setting state that filament wherein 7 is formed up to the second layer 5 be ' 2 ', and wherein filament 7 formation are ' 3 ' up to the 3rd layer 6 setting state, and many-valued electro-resistance element 10 is provided.
Can also be through the control threshold voltage so that exist a plurality of following zones that the electro-resistance element with bigger value number is provided in the oxide skin(coating) 1: concentration gradient all has peak value in each of said a plurality of zones.
The favourable amount that obtains the required O that in oxide skin(coating) 1, comprises of many-valued electro-resistance element 10 will be described below.For the purpose of simplifying the description, through supposing that two layers (first and second layers) with different oxygen concentrations that between electrode 2 and electrode 3, form as shown in Figure 5 describe.Just, in oxide skin(coating) 1, there is a concentration gradient peak value.
As stated, for through the metal of electrode 2 is spread applying voltage between electrode 2 and 3 as ion, in oxide skin(coating) 1, form filament 7 according to the operation principle of the electro-resistance element 10 of this embodiment thus in oxide skin(coating) 1.According to the result of the research of being undertaken by the inventor, can form filament 7 through 100ns or littler fast potential pulse.This shows that the metal ion of formation filament does not spread with slow relatively diffusion form (for example, room crossover or lattice displacement type diffusion form) but spreads with gap insert type diffusion form.Just, the metal ion that forms filament 7 spreads under electriferous state, because jump (hop) between the lattice of metal ion in oxide skin(coating) 7.Under this state, the easness of the diffusion of metal ion in oxide skin(coating) 1 is confirmed by the easness of the jump of metal ion usually.Just, the jump rate of metal ion (hopping rate) ν (S -1) be expressed from the next:
v = v 0 exp ( - E A kT ) . . . ( 1 )
ν wherein 0(S -1) be attempt frequency (attempt frequency) of jumping and the value that is equivalent to about debye (Debye) frequency, E ABe the required activation energy that jumps.The metal that forms filament 7 is pulled to oxide skin(coating) 1 inside through electric field.Just, owing to metal moves because of being shifted onto in the oxide skin(coating) 1 by electric field, the easness that therefore moves and the ionic radius of metal have close relation.Just, ionic radius is big more, and the gap required activation energy that jumps is high more.
Fig. 6 is the figure that shows the ionic radius of metal.The representative of using Ag and Cu as these metals is described.
The condition of the O content in oxide skin(coating) 1 that can realize many-valued operation will be described below.First-selection is with the state (initial condition) that wherein in oxide skin(coating) 1, does not form filament 7 is described.When between electrode 2 and 3, applying voltage under this state, be included in the diffusion flux J of the metal reason following formula indication in the electrode 2 Top(A) and J Mid(A) in oxide skin(coating) 1, spread:
J Top = q Ev Top = q Ev 0 Exp ( - E A KT ) (ground floor) ... (2)
j Mid = q E ′ v Mid = q E ′ v 0 Exp ( - E A ′ KT ) (second layer) ... (3)
Wherein k is a Boltzmann constant, and T is temperature (K), E AAnd E' ABe the jump activation energy (eV) of metal ion in first and second layers, and E and E' are applied to first and second layers electric field (V/cm).
Next, explanation is wherein formed the state of filament 7 in ground floor.When in ground floor, forming filament 7, form part and become conduction, therefore voltage drop do not appear in ground floor.Therefore, owing to the effect that reduces to obtain owing to the film thickness that it is applied voltage, the electric field that is applied to the second layer raises.Therefore, in ground floor, form filament 7 diffusion flux J afterwards Mid' be expressed from the next:
J mid ′ = q E ′ ′ v mid = q E ′ ′ v 0 exp ( - E A ′ kT ) . . . ( 4 )
(second layer in ground floor under the state of formation filament)
Because E' E ", the rising of this electric field has increased the diffusion flux of charged ion.If the diffusion flux that promptly is engraved in the second layer before beginning to set is equal to or greater than the diffusion flux in ground floor, that is,, then can not realize many-valued operation if the diffusion flux in the second layer is in the state by the following formula indication.
q E ′ ′ v 0 exp ( - E A ′ kT ) ≥ q Ev 0 exp ( - E A kT ) . . . ( 5 )
This be because, it is easier than diffusion in ground floor that metal ion forms in the second layer before the filament 7, therefore the formation of filament 7 can not stop in the second layer, charged ion spreads in the second layer and formation filament 7 equally.
Under this state, can not realize the many-valued operation that this embodiment is intended to.Therefore, even when filament 7 forms in ground floor, there is not metal ion to be diffused into the condition of the condition of the second layer for the many-valued operation of realization yet.This condition is indicated by following formula.
q E &prime; &prime; v 0 exp ( - E A &prime; kT ) < < q Ev 0 exp ( - E A kT ) . . . ( 6 )
In order in oxide skin(coating) 1, accurately to form filament 7, diffusion flux preferably changes an one magnitude or more, and this condition is indicated by following formula.
Figure BDA00002090742300084
&DoubleLeftRightArrow; exp ( E A - E A &prime; kT ) < 1 10 . . . ( 8 )
&DoubleLeftRightArrow; E A &prime; - E A > kT ln ( 1 10 ) . . . ( 9 )
Because working temperature is room temperature (300K), according to calculating, the poor (E' of activation energy A-E A) be necessary for 0.06eV or bigger.Just, if the difference between the activation energy that jumps in the gap of the metal ion between first and second layers is 0.06eV, the many-valued operation that can realize this embodiment reliably and be intended to.In this embodiment, control activation energy through the concentration that changes the O that in first and second layers, comprises.
For example, Si that when electrode is processed by Cu many-valued operation is required and the content of O will be described below.The activation energy of diffusion of the Cu ion in Si (O content=0%) is 0.18eV.By contrast, at SiO 2Activation energy in (O content=67%) is 1.2eV.When inserting, activation energy is changed into 4% from what above-mentioned value changed the required O content of 0.06eV.Just, when the O content in the second layer than the O content in the ground floor high 4% or when bigger, can realize many-valued operation.
When using the Ag ion, at SiO 2Activation energy in (O content=67%) is 1.3eV.And the activation energy in Si is 0.87eV.In this case, when the O content difference be 9.3% or when bigger, many-valued operation is possible.
Usually, (this method is called electric current hereinafter and is obedient to method (current compliance method) to form filament through the value of controlling the electric current that will be fed to electro-resistance element.Yet, be obedient in the method at electric current, owing to the electric current that for example flows into from the parasitic capacitance of the wiring that is connected to electro-resistance element has big influence to the reliability of element, filament is difficult to form.
Because the influence of the parasitic capacitance that when forming filament, connects up is especially big, therefore must near electro-resistance element, form transistor accurately forms filament to be obedient to method through electric current.Correspondingly, the electric current method of the being obedient to size that is not suitable for electro-resistance element reduces (downsizing).In addition, the electric current method of being obedient to produces Joule heat in oxide skin(coating).If electro-resistance element is set to located adjacent one another, therefore, can change the composition of the oxide skin(coating) in the contiguous electro-resistance element by the heat of given electro-resistance element generation.
On the other hand, according to the electro-resistance element 10 working voltages control of this embodiment and the metal ion diffusion velocity difference that causes by the concentration difference in the oxide skin(coating) 1.This makes can realize many-valued operation through voltage control, and eliminates the needs that form any extra transistor.Correspondingly, compare, can form filament more accurately with using the conventional current method of being obedient to.
Next, with the manufacturing approach of explanation according to the electro-resistance element 10 of this embodiment.
At first with the accelerating voltage and 2 * 10 of for example 30keV 15Cm -2Dosage the B ion is injected in the electrode of processing by the Si single crystalline substrate 3, the line activating of going forward side by side annealing forms p type Si zone thus.
Then, the oxide skin(coating) of processing by Si through for example CVD (chemical vapour deposition (CVD)) deposition 1.In this step, through the SiH of adjustment as source gas 4The flowing velocity ratio of oxygen is come the ratio of the O in the controlled oxidation thing layer 1.In the structure of this embodiment, O content reduces from the orlop of the multilayer film of oxide skin(coating) 1 successively.For example, O content is followed successively by 20%, 10% and 0.5% from orlop.Can analyze O content through for example XPS (x-ray photoelectron spectroscopy), SIMS (secondary ion mass spectroscopy) or TEM-EDS (transmission electron microscopy-energy dispersion spectrum).
Afterwards, the electro-resistance element 10 that the electrode of being processed by Ag through deposition 2 obtains according to this embodiment.
Embodiment has been described above.Note, under the situation of spirit that does not deviate from the basis design and scope, can carry out various modifications and change embodiment.
Embodiment also relates to the technology of electro-resistance element self, and can be applicable to any circuit and do not consider to connect the method for electro-resistance element.
As shown in Figure 7, an instance is so-called joining type memory array, wherein following wiring and on each intersection of wiring form electro-resistance element 10 and rectifier cell (rectifier cell more specifically is the diode element such as the P-I-N diode).In this is provided with, forms wiring along column direction, and follow direction and form down wiring.The operation principle of this memory cell array is for being applied to voltage through selecting in the wiring and descending an electro-resistance element 10 as record object in the wiring.More specifically, control part is applied to selected go up wiring and wiring down with free voltage.
When electro-resistance element has rectification function, then can omit rectifier cell.
As shown in Figure 8; Another instance is three sandwich constructions (resistance variations devices), and wherein oxide skin(coating) 1 is sandwiched in through on the substrate (not shown) alternately between the structure (first lamination) that forms of multilayer electrode 2 and insulating barrier 8 and the structure (second lamination) that forms through alternately laminated electrode 3 and dielectric film 8.In this structure, electrode 3 is formed towards electrode 2, and each of electrode 2 and 3 is to forming filament 7.Dielectric film 8 is by for example Al 2O 3Or SiO 2Process.
Fig. 9 illustrates the instance of resistance variations memory.
The memory cell array has transistor-an element (one transistor-one element) type.
Word line WL I-1, WL iAnd WL I+1Extend bit line UBL along directions X J-1, UBL j, UBL J+1, LBL J-1, LBL jAnd LBL J+1Extend along the Y direction.
Word line WL I-1, WL iAnd WL I+1In each a end be connected to word line driver and decoder 11 through MOS transistor RSW as selector switch.Bit line UBL J-1, UBL j, UBL J+1In each a end be connected to bit line driver/transducer (sinker) and decoder and read circuit 12A.Bit line LBL J-1, LBL jAnd LBL J+1In each a end be connected to bit line driver/transducer and decoder 12B.
Be used to select the selection signal R of a word line (OK) I-1, R iAnd R I+1Be imported into the grid of MOS transistor RSW.Bit line driver/transducer and decoder with read circuit 12A and have and select bit line UBL J-1, UBL j, UBL J+1In one function.Bit line driver/transducer and decoder with read circuit 12B and have and select bit line LBL J-1, LBL jAnd LBL J+1In one function.
Via source electrode and the drain electrode of MOS transistor T, a terminal of memory cell 13 is connected to bit line UBL J-1, UBL jAnd UBL J+1In corresponding one, and the another terminal of memory cell 13 is connected to bit line LBL J-1, LBL jAnd LBL J+1In corresponding one.The grid of MOS transistor T is connected to word line WL I-1, WL iAnd WL I+1
In this structure, a MOS transistor T is connected to a memory cell 13.Therefore, can not appear at the sneak-out current (sneak current) that causes problem in the intersection point type, therefore can improve the read/write reliability.
Figure 10 shows the structure of the part X among Fig. 9.
MOS transistor T is formed on the Semiconductor substrate 100.One in the source electrode of MOS transistor T and the drain electrode is connected to bit line UBL through memory cell 13 (1) jIn the source electrode of MOS transistor T and the drain electrode another is connected to bit line LBL j
Memory cell 13 is the electro-resistance element of embodiment.Therefore, a memory cell 13 can be stored and have three or more many-valued multi-value data.
Being characterized as of an above-mentioned transistor-a primitive type can improve the read/write reliability, and this is because a MOS crystal is connected to each memory cell 13.Can also be through improving for example word line WL I-1, WL iAnd WL I+1And bit line UBL J-1, UBL j, UBL J+1, LBL J-1, LBL jAnd LBL J+1Layout (layout), improve the integrated level of memory cell 13.
Though described specific embodiment, these embodiment only provide through instance, are not intended to limit the scope of the invention.In fact, the novel embodiment that describes among this paper can various other embodied; In addition, under the situation that does not deviate from spirit of the present invention, the embodiment that can describe in this article carries out various omissions in form, substitutes and changes.Accompanying claims and equivalent thereof are intended to contain such form or the modification that falls in scope of the present invention and the spirit.

Claims (21)

1. resistance variations device comprises:
First electrode that comprises metal;
Second electrode; And
The amorphous oxide layer that comprises Si and O between said first and second electrodes, this layer have the concentration gradient and first peak value thereof of O in the direction from said first electrode to said second electrode.
2. according to the device of claim 1,
Wherein, said oxide skin(coating) has along second peak value of the said concentration gradient of said direction.
3. according to the device of claim 1,
Wherein, said oxide skin(coating) has along a plurality of peak values that comprise said first peak value of the said concentration gradient of said direction.
4. according to the device of claim 1,
Wherein, said device is stored multi-value data through the voltage between said first and second electrodes being changed to of being selected from two or more values that differ from one another.
5. according to the device of claim 4,
Wherein, the value of said multi-value data is confirmed by the length of that provide between said first and second electrodes and filament that comprise said metal.
6. according to the device of claim 1,
Wherein, said metal is a kind of among Ag, Ti, Ni, Co, Al, Cr, Cu, W, Hf, Ta and the Zr.
7. according to the device of claim 1,
Wherein, said second electrode is the Si that is doped with impurity.
8. memory cell array comprises:
A plurality of first wirings, it comprises metal and extends to first direction;
A plurality of second wirings, it is to extending with the crossing second direction of said first direction; And
A plurality of memory cells, it is set between said first and second wirings, and each in said a plurality of memory cells comprises electro-resistance element,
Wherein, said electro-resistance element comprises the amorphous oxide layer that comprises Si and O, and on the third direction that intersects with said first and second directions, has the concentration gradient and first peak value thereof of O.
9. according to Claim 8 array,
Wherein, said oxide skin(coating) has along second peak value of the said concentration gradient of said third direction.
10. according to Claim 8 array,
Wherein, said oxide skin(coating) has along a plurality of peak values that comprise said first peak value of the said concentration gradient of said third direction.
11. array according to Claim 8,
Wherein, a selected memory cell in said a plurality of memory cell changes to of being selected from two or more values that differ from one another through the voltage between selected second in selected first wiring in said a plurality of first wirings and said a plurality of second wirings are connected up and stores multi-value data.
12. according to the array of claim 11,
Wherein, the value of said multi-value data is confirmed by that provide between said selected first wiring and said selected second wiring and length filament that comprise said metal.
13. array according to Claim 8,
Wherein, said metal is a kind of among Ag, Ti, Ni, Co, Al, Cr, Cu, W, Hf, Ta and the Zr.
14. array according to Claim 8,
Wherein, said second wiring is for being doped with the Si of impurity.
15. a resistance variations device comprises:
A plurality of first electrodes, each said first electrode package containing metal and along the first direction setting;
A plurality of second electrodes, it is along said first direction setting, and on the second direction that intersects with said first direction one by one towards each said first electrode; And
The amorphous oxide layer that comprises Si and O between said first electrode and said second electrode, this layer have the concentration gradient and first peak value thereof of O on said second direction.
16. according to the device of claim 15,
Wherein, said oxide skin(coating) has along second peak value of the said concentration gradient of said second direction.
17. according to the device of claim 15,
Wherein, said oxide skin(coating) has along a plurality of peak values that comprise said first peak value of the said concentration gradient of said second direction.
18. according to the device of claim 15,
Wherein, said device is stored multi-value data through the voltage between said first electrode and said second electrode being changed in the part of coming between said first electrode and said second electrode that is selected from two or more values that differ from one another.
19. according to the device of claim 18,
Wherein, the value of said multi-value data is confirmed by that provide between one in one in said first electrode and said second electrode and length filament that comprise said metal.
20. according to the device of claim 15,
Wherein, said metal is a kind of among Ag, Ti, Ni, Co, Al, Cr, Cu, W, Hf, Ta and the Zr.
21. according to the device of claim 15,
Wherein, said second electrode is the Si that is doped with impurity.
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